CN110284139A - Etchant composition and method of fabricating metal pattern and array substrate using the same - Google Patents
Etchant composition and method of fabricating metal pattern and array substrate using the same Download PDFInfo
- Publication number
- CN110284139A CN110284139A CN201910207694.9A CN201910207694A CN110284139A CN 110284139 A CN110284139 A CN 110284139A CN 201910207694 A CN201910207694 A CN 201910207694A CN 110284139 A CN110284139 A CN 110284139A
- Authority
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- China
- Prior art keywords
- etching agent
- agent composite
- cycle
- compound
- azo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 136
- 239000002184 metal Substances 0.000 title claims abstract description 136
- 239000000758 substrate Substances 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title abstract description 21
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 115
- 239000010949 copper Substances 0.000 claims abstract description 71
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052802 copper Inorganic materials 0.000 claims abstract description 60
- 239000010936 titanium Substances 0.000 claims abstract description 46
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 45
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- -1 carbonyl ring compound Chemical class 0.000 claims abstract description 25
- 238000005530 etching Methods 0.000 claims description 245
- 150000001875 compounds Chemical class 0.000 claims description 230
- 239000003795 chemical substances by application Substances 0.000 claims description 199
- 239000002131 composite material Substances 0.000 claims description 189
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 65
- 238000000034 method Methods 0.000 claims description 57
- 150000002222 fluorine compounds Chemical class 0.000 claims description 36
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 32
- VFNGKCDDZUSWLR-UHFFFAOYSA-L disulfate(2-) Chemical compound [O-]S(=O)(=O)OS([O-])(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-L 0.000 claims description 29
- 229910019142 PO4 Inorganic materials 0.000 claims description 23
- 239000010452 phosphate Substances 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 23
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 10
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 10
- 125000004122 cyclic group Chemical group 0.000 claims description 9
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 7
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 7
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 7
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 6
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 6
- ZOBPZXTWZATXDG-UHFFFAOYSA-N 1,3-thiazolidine-2,4-dione Chemical compound O=C1CSC(=O)N1 ZOBPZXTWZATXDG-UHFFFAOYSA-N 0.000 claims description 5
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 5
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 5
- 229940123464 Thiazolidinedione Drugs 0.000 claims description 5
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 5
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 5
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- 229960002317 succinimide Drugs 0.000 claims description 5
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 102000004377 Thiopurine S-methyltransferases Human genes 0.000 claims description 4
- 108090000958 Thiopurine S-methyltransferases Proteins 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 4
- UTEFBSAVJNEPTR-RGEXLXHISA-N loprazolam Chemical compound C1CN(C)CCN1\C=C/1C(=O)N2C3=CC=C([N+]([O-])=O)C=C3C(C=3C(=CC=CC=3)Cl)=NCC2=N\1 UTEFBSAVJNEPTR-RGEXLXHISA-N 0.000 claims description 4
- 229960003019 loprazolam Drugs 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 3
- 229910002567 K2S2O8 Inorganic materials 0.000 claims description 3
- 229910004882 Na2S2O8 Inorganic materials 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 235000003270 potassium fluoride Nutrition 0.000 claims 1
- 239000010410 layer Substances 0.000 description 146
- 230000000052 comparative effect Effects 0.000 description 36
- 230000008569 process Effects 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 10
- 238000009825 accumulation Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- 102100036464 Activated RNA polymerase II transcriptional coactivator p15 Human genes 0.000 description 8
- 101000713904 Homo sapiens Activated RNA polymerase II transcriptional coactivator p15 Proteins 0.000 description 8
- 229910004444 SUB1 Inorganic materials 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000003628 erosive effect Effects 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000003918 potentiometric titration Methods 0.000 description 6
- 239000002516 radical scavenger Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000001469 hydantoins Chemical class 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OMAFFHIGWTVZOH-UHFFFAOYSA-O 1-methyl-2h-tetrazol-1-ium Chemical compound C[N+]1=CN=NN1 OMAFFHIGWTVZOH-UHFFFAOYSA-O 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000003682 fluorination reaction Methods 0.000 description 4
- HPCCWDVOHHFCKM-UHFFFAOYSA-M lithium;hydrogen sulfate Chemical compound [Li+].OS([O-])(=O)=O HPCCWDVOHHFCKM-UHFFFAOYSA-M 0.000 description 4
- 208000009242 medullary sponge kidney Diseases 0.000 description 4
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229940123457 Free radical scavenger Drugs 0.000 description 3
- 229910004438 SUB2 Inorganic materials 0.000 description 3
- 101100311330 Schizosaccharomyces pombe (strain 972 / ATCC 24843) uap56 gene Proteins 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 101150018444 sub2 gene Proteins 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KNRUQUSSDKZTSQ-UHFFFAOYSA-O 1h-tetrazol-1-ium-1-amine Chemical compound NN1C=[NH+]N=N1 KNRUQUSSDKZTSQ-UHFFFAOYSA-O 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical group [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000004172 nitrogen cycle Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001303 quality assessment method Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- TYHJXGDMRRJCRY-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) tin(4+) Chemical compound [O-2].[Zn+2].[Sn+4].[In+3] TYHJXGDMRRJCRY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/124—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or layout of the wiring layers specially adapted to the circuit arrangement, e.g. scanning lines in LCD pixel circuits
- H01L27/1244—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or layout of the wiring layers specially adapted to the circuit arrangement, e.g. scanning lines in LCD pixel circuits for preventing breakage, peeling or short circuiting
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/02—Local etching
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136286—Wiring, e.g. gate line, drain line
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32139—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer using masks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1259—Multistep manufacturing methods
- H01L27/1288—Multistep manufacturing methods employing particular masking sequences or specially adapted masks, e.g. half-tone mask
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136286—Wiring, e.g. gate line, drain line
- G02F1/136295—Materials; Compositions; Manufacture processes
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- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/124—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or layout of the wiring layers specially adapted to the circuit arrangement, e.g. scanning lines in LCD pixel circuits
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- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1259—Multistep manufacturing methods
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Abstract
The etchant composition of an embodiment of the present invention includes a persulfate, a tetra-nitrogen ring compound, a carbonyl ring compound having two or more carbonyl groups, and water, and a weight ratio of the tetra-nitrogen ring compound and the carbonyl ring compound is about 1:0.1 to about 1: 2. The etchant composition can etch a titanium/copper multilayer and can be used to manufacture a metal pattern and an array substrate having excellent etch pattern characteristics.
Description
Cross reference to related applications
Patent application claims are on March 19th, 2018 South Korea patent application submitted the 10-2018-0031722nd
Priority, entire contents are incorporated herein by reference.
Technical field
Disclosure herein is related to etching agent composite and using etching agent composite manufacture metal pattern and array base
The method of plate, and more particularly, to the etching agent composite provided for etching multiple metal layers and use the etchant
The method of composition manufacture metal pattern and array substrate.
Background technique
According to the requirement in flat panel display industry for realizing high-resolution, large scale and 3D display, to quick response
The needs of rate are continuously increased.Especially, in order to realize high-resolution, it is desirable that reduce electricity used in the circuit board of display device
The width of the metal pattern of line, and in this case, in order to control resistance value, the height of pattern increases, and therefore goes out
The defect of the poor step coverage of existing laminated metal layer.
Meanwhile as metallic pattern material, using the friendly copper of the ecology with excellent conductivity, and in order to increase
Using the adhesion strength of the metal pattern middle high-resolution of copper, another metal layer apart from copper is used as the case where bottom and is increased
It is more.Etching therefore, it is necessary to the cone angle appropriate that can remain adapted to make to include the multi-layered patterned of layers of copper and etch in batch
Agent composition.
Summary of the invention
Present disclose provides etching agent composite, it is used to make to include multi-layered patterned period of copper providing excellent cone
Bulk properties.
The disclosure additionally provides the method for manufacturing the various metals pattern with excellent taper.In addition, the disclosure
The method for manufacturing array substrate is additionally provided, by being formed there is the various metals pattern of excellent taper to reduce cloth
Line defect, such as short circuit.
The embodiment of present inventive concept provides etching agent composite, based on the total amount of the etching agent composite, institute
Stating etching agent composite includes persulfate of the about 5wt% to about 20wt%；Four-azo-cycle the chemical combination of about 0.1wt% to about 2wt%
Object；The carbonyl cycle compound with two or more carbonyls of about 0.01wt% to about 3wt%；And water, wherein four-azo-cycles
The weight ratio for closing object and carbonyl cycle compound is about 1:0.1 to about 1:2.
In one embodiment, etching agent composite can further comprise more than or equal to about 0.01wt% and being less than about
Three-the azo-cycle compounds with sulfydryl of 1wt%.
In one embodiment, the weight ratio of carbonyl cycle compound and three-azo-cycle compounds can be about 1:0.2 to about 1:
2。
In one embodiment, etching agent composite can further comprise hydrogen sulfate of the about 0.1wt% to about 5wt%
Salt.
In one embodiment, etching agent composite can further comprise that the fluorination of about 0.01wt% to about 2wt% is closed
Object.
In one embodiment, etching agent composite can further comprise the sulfonic acid chemical combination of about 0.1wt% to about 5wt%
Object.
In one embodiment, etching agent composite can further comprise about 0.01wt% to the phosphoric acid of about 5wt% or
Phosphate.
In one embodiment, based on the total amount of etching agent composite, etching agent composite can further comprise about
The fluorine compounds of 0.01wt% to about 2wt%；Three-the azo-cycle compounds with sulfydryl of about 0.01wt% to about 1wt%；About
The disulfate of 0.1wt% to about 5wt%；The sulfoacid compound of about 0.1wt% to about 5wt%；About 0.01wt% is to about
The phosphoric acid or phosphate of 5wt%.
In one embodiment, persulfate may include potassium peroxydisulfate (K2S2O8), sodium peroxydisulfate (Na2S2O8) and over cure
Sour ammonium ((NH4)2S2O8At least one of).
In one embodiment, four-azo-cycle compounds may include in Aminotetrazole, methyl tetrazolium and thiopurine methyltransferase tetrazolium
It is at least one.
In one embodiment, carbonyl cycle compound may include in thiazolidinedione, hydantoins and succinimide
At least one.
In one embodiment, fluorine compounds may include hydrogen fluoride (HF), ammonium fluoride (NH4F), potassium fluoride (KF), fluorine
Change sodium (NaF), ammonium acid fluoride (F2H5N), potassium hydrogen fluoride (KHF2) and sodium bifluoride (NaHF2At least one of).
In one embodiment, the three-azo-cycle compounds with sulfydryl may include 3- sulfydryl -4- methyl -4H-1,2,4-
At least one of triazole, 3- amino -1,2,4- triazole -5- mercaptan and 1H-1,2,4- triazole -3- mercaptan.
In one embodiment, disulfate may include ammonium hydrogen sulfate (NH4HSO4), lithium hydrogen sulfate (LiHSO4), sulfuric acid
Hydrogen potassium (KHSO4) and sodium bisulfate (NaHSO4At least one of).
In one embodiment, sulfoacid compound may include Loprazolam, benzene sulfonic acid, p-methyl benzenesulfonic acid, ichthyodin, ammonia
Base sulfonic acid, cyclic annular at least one of sulfoacid compound and the sulfoacid compound based on hydrocarbon.
In the embodiment of present inventive concept, the method for manufacturing metal pattern is provided, this method comprises: wrapping
It includes and forms light sensitive layer pattern in the multilayer of titanium and copper；To form the multi-layer lifting of light sensitive layer pattern thereon for etching agent composite；With
Light sensitive layer pattern is removed, wherein etching agent composite includes persulfate, four-azo-cycle compounds, has two or more carbonyls
The carbonyl cycle compound and water of base, and the weight ratio of four-azo-cycle compounds and carbonyl cycle compound is about 1:0.1 to about 1:
2。
In one embodiment, multilayer can include: the first metal layer comprising titanium；On the first metal layer simultaneously with setting
And the second metal layer including copper, wherein etching agent composite etches the first metal layer and second metal layer in batch mode.
In one embodiment, etching agent composite can further comprise three-azo-cycle compounds, the sulfuric acid with sulfydryl
Hydrogen salt, fluorine compounds, sulfoacid compound and phosphoric acid or phosphate, and the total amount based on etching agent composite, etchant combination
Object may include persulfate of the about 5wt% to about 20wt%；Four-the azo-cycle compounds of about 0.1wt% to about 2wt%；About
The carbonyl cycle compound of 0.01wt% to about 3wt%；The fluorine compounds of about 0.01wt% to about 2wt%；About 0.01wt% is to about
Three-the azo-cycle compounds of 1wt%；The disulfate of about 0.1wt% to about 5wt%；About 0.1wt% is sulfonated to about 5wt%'s
Close object；The phosphoric acid or phosphate of about 0.01wt% to about 5wt%；With the water of surplus.
In the embodiment of present inventive concept, the method for manufacturing array substrate is provided, this method comprises: in base
Grid line and gate electrode connected to the gate line are formed on plate；It is formed in an insulated state across the data line of grid line, with data
The source electrode of line connection, and the drain electrode separated with source electrode；The pixel electrode being connect with formation with drain electrode, wherein forming grid
Polar curve and gate electrode connected to the gate line include: to form light sensitive layer pattern in the multilayer for including titanium and copper；To be formed thereon
The multi-layer lifting of light sensitive layer pattern is for etching agent composite；With removal light sensitive layer pattern, wherein etching agent composite includes persulfuric acid
Salt, four-azo-cycle compounds, carbonyl cycle compound and water with two or more carbonyls, and four-azo-cycle compounds and
The weight ratio of carbonyl cycle compound is about 1:0.1 to about 1:2.
In one embodiment, etching agent composite can further comprise three-azo-cycle compounds, the sulfuric acid with sulfydryl
Hydrogen salt, fluorine compounds, sulfoacid compound and phosphoric acid or phosphate, and the total amount based on etching agent composite, etchant combination
Object may include persulfate of the about 5wt% to about 20wt%；Four-the azo-cycle compounds of about 0.1wt% to about 2wt%；About
The carbonyl cycle compound of 0.01wt% to about 3wt%；The fluorine compounds of about 0.01wt% to about 2wt%；About 0.01wt% is to about
Three-the azo-cycle compounds of 1wt%；The disulfate of about 0.1wt% to about 5wt%；About 0.1wt% is sulfonated to about 5wt%'s
Close object；The phosphoric acid or phosphate of about 0.01wt% to about 5wt%；With the water of surplus.
Detailed description of the invention
Present inventive concept is further understood with providing including attached drawing, and attached drawing is incorporated in this specification and constitutes this
Part of specification.Attached drawing shows the illustrative embodiments of present inventive concept, and is used to explain this together with specification
The principle of inventive concept.In the accompanying drawings:
Figure 1A to 1E is the metal pattern that display manufactures embodiment using the etching agent composite of embodiment in order
Method the step of viewgraph of cross-section；
Fig. 2 is a pixel of the display device including array substrate for the embodiment that display is conceived according to the present invention
Plan view；
Fig. 3 is the cross-sectional view along the line I-I ' interception in Fig. 2；
Fig. 4 shows the electronic scanner microscope image on the metal pattern of embodiment；And
Fig. 5 A and 5B respectively illustrate embodiment and compare the electronic scanner microscope on the metal pattern of embodiment
Image.
Specific embodiment
Present inventive concept can embody in different forms and may have various modifications, and below with reference to the accompanying drawings more in detail
The illustrative embodiments of present inventive concept carefully are described.However, present inventive concept should not be construed as limited by the reality illustrated herein
Apply mode.But these embodiments be understood to include modification in the spirit and scope of present inventive concept, equivalent way or
Replacement.
In the accompanying drawings, identical referential data always shows identical element.For clarity, it is exaggerated the ruler of structure
It is very little.It will be appreciated that though term first, second etc. can be used to describe herein various elements, but these elements should not be by
The limitation of these terms.These terms are only used to distinguish an element and another element.Therefore, without departing substantially from present invention teach that
In the case where, the first element can be described as the second element.Similarly, the second element can be described as the first element.As used herein, single
Number form formula is also intended to including plural form, unless the context clearly indicates otherwise.
It is to be further understood that term " including (comprises) " and/or " including (comprising) ", in this specification
In in use, show in the presence of narration feature, numerical value, step, operation, element, components or groups thereof, but do not exclude the presence of or
Add one or more other features, numerical value, step, operation, element, components or groups thereof.
It in the disclosure, can " direct " when layer, film, region, plate etc. are referred to as at another component "upper" or " top "
In another component "upper", or middle layer also may be present.Rather, it should be appreciated that when layer, film, region, plate etc. are referred to as another
When component "lower" or " lower section ", can " direct " in another component " lower section ", and one or more middle layers also may be present.Separately
Outside, it is also to be understood that may be provided in above or below another component when plate is known as being arranged at another component " top ".
Hereafter, the etching agent composite for the embodiment conceived according to the present invention will be explained.
The etching agent composite for the embodiment conceived according to the present invention can be used for etching metal layer to form metal pattern.
The etching agent composite for the embodiment conceived according to the present invention can be used for etching the multilayer including copper (Cu) and titanium (Ti).Example
Such as, it can be used for etching according to the etching agent composite of embodiment and wherein stack the titanium coating including titanium and the copper gold including copper
Belong to the multilayer of layer, to form metal pattern.Especially, multilayer can stack in order double for wherein titanium coating and copper metal layer
Layer.
The etching agent composite of embodiment may include persulfate, four-azo-cycle compounds, have two or more carbonyls
Carbonyl cycle compound, fluorine compounds and the water of base.
In the etching agent composite of embodiment, persulfate is primary oxidizers and can be for for etching including copper
Metal layer etchant.However, the embodiment of present inventive concept is without being limited thereto, and it includes titanium that persulfate is etchable
Metal layer.
Total amount based on etching agent composite, the amount for the persulfate that may include are about 5wt% to about 20wt%.For example,
Total amount based on etching agent composite, the amount for the persulfate that may include are about 10wt% to about 20wt%.Especially, based on erosion
The total amount of agent composition is carved, the amount for the persulfate that may include is about 10wt% to about 18wt%.
If the amount of persulfate is greater than about 20wt%, the erosion of the metal layer of the etching agent composite of embodiment is used
Etching speed may be too fast, and is likely difficult to control etching degree, and therefore, the metal layer including copper can be by overetch.Separately
Outside, if the amount of persulfate is less than about 5wt%, etch-rate may decline, and the etching carried out may be insufficient.
Persulfate can be potassium peroxydisulfate (K2S2O8), sodium peroxydisulfate (Na2S2O8) or ammonium persulfate ((NH4)2S2O8).It is real
The etching agent composite for applying mode may include at least one of potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate as persulfuric acid
Salt.That is, the etching agent composite of embodiment may include any one of potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate or
Two or more are as persulfate.
The etching agent composite of embodiment includes four-azo-cycle compounds.Four-azo-cycle compounds can prevent the corrosion of copper simultaneously
And the surface profile of the copper of etching can be stably kept.It includes four nitrogen originals in the atom of ring that four-azo-cycle compounds, which mean to be formed,
The compound of son.
Total amount based on etching agent composite, the amount for the four-azo-cycle compounds that may include are about 0.1wt% to about 2wt%.
For example, the total amount based on etching agent composite, the amount for the four-azo-cycle compounds that the etching agent composite of embodiment may include are
About 0.1wt% to about 1wt%.Especially, based on the total amount of etching agent composite, the etching agent composite of embodiment may include
The amounts of four-azo-cycle compounds be about 0.2wt% to about 0.7wt%.
If the amount of four-azo-cycle compounds is greater than about 2wt%, due to the influence of excessive four-azo-cycle compound, etching
Rate may decline, and may be declined using the processability of the etch process of the etching agent composite of embodiment.In addition, such as
The amount of four-azo-cycle compound of fruit is less than about 0.1wt%, then the etch-rate of the metal layer including copper may be excessively increased, and
It is likely difficult to the etching degree of control metal layer.
Four-azo-cycle compounds can be substituted or unsubstituted tetrazole compound.For example, four-azo-cycle compounds can be amino
Tetrazolium, methyl tetrazolium or thiopurine methyltransferase tetrazolium.The etching agent composite of embodiment may include Aminotetrazole, methyl tetrazolium and mercapto first
At least one of base tetrazolium is used as four-azo-cycle compounds.That is, the etching agent composite of embodiment may include Aminotetrazole,
Any one of methyl tetrazolium and thiopurine methyltransferase tetrazolium or two or more as four-azo-cycle compounds.
The etching agent composite of embodiment includes the carbonyl cycle compound with two or more carbonyls.In specification
In, carbonyl cycle compound include carbonyl carbon atom as cycle compound at ring carbon, and at this carbonyl for including in ring carbon
Base is two or more.For example, in one embodiment, carbonyl cycle compound can have that there are two carbonyls, and in particular, can
Become the cyclic compound of ring carbons for the carbon atom of two of them carbonyl.
The carbonyl cycle compound for including in the etchant of embodiment can play the role of potentiometric titrations scavenger, removal
The potentiometric titrations generated during etching copper metal layer.The persulfate for including in the etchant of embodiment is in etch copper gold
Potentiometric titrations are generated during belonging to layer, and four-azo-cycle compounds can be attacked and be decomposed to the potentiometric titrations generated.Separately
Outside, four-azo-cycle compounds of decomposition can be by partial adsorbates on copper metal layer, to reduce the etching of etching agent composite
Energy.Therefore, if the etching agent composite of embodiment includes carbonyl cycle compound, carbonyl cycle compound inhibits four-azo-cycles
The decomposition of compound and the etching performance that etching agent composite can be improved.
Total amount based on etching agent composite, the amount for the carbonyl cycle compound with two or more carbonyls that may include
It is about 0.01wt% to about 3wt%.For example, the total amount based on etching agent composite, the etching agent composite of embodiment can be wrapped
The amount of the carbonyl cycle compound contained is about 0.01wt% to about 1wt%.Especially, based on the total amount of etching agent composite, implement
The amount for the carbonyl cycle compound that the etching agent composite of mode may include is about 0.01wt% to about 0.5wt%.
If the amount of carbonyl cycle compound is greater than about 3wt%, carbonyl cycle compound can be adsorbed on metal layer and
The etching performance of etching agent composite may decline.In addition, if the amount of carbonyl cycle compound is less than about 0.01wt%, carbonyl
The free radical scavenger function of cycle compound may be insufficient, possibly can not inhibit four-azo-cycle compounds in etching agent composite
It decomposes, and etching performance may decline.
Carbonyl cycle compound can be thiazolidinedione, hydantoins or succinimide.The etchant combination of embodiment
Object may include that at least one of thiazolidinedione, hydantoins and succinimide are used as carbonyl cycle compound.For example, implementing
The etching agent composite of mode may include any one of thiazolidinedione, hydantoins and succinimide or two kinds or
It is more kinds of to be used as carbonyl cycle compound.
In the etching agent composite of embodiment, the weight ratio of four-azo-cycle compounds and carbonyl cycle compound can be about
1:0.1 to about 1:2.Relative to the weight ratio 1 of four-azo-cycle compounds, closed when the carbonyl with two or more carbonyls is cyclized
When the weight ratio of object is less than 0.1, then carbonyl cycle compound possibly can not play the role of free radical scavenger, and etching performance
It may decline.Relative to the weight ratio 1 of four-azo-cycle compounds, when the carbonyl cycle compound with two or more carbonyls
When weight ratio is greater than 2, then the characterization of adsorption of carbonyl cycle compound on the metal layer may enhance, and etching quality may
Deterioration.
The etching agent composite of embodiment includes fluorine compounds.Fluorine compounds mean include fluorine (F) atom fluoride.
Fluorine compounds can be the etchant for etching the metal layer including titanium.However, the embodiment of present inventive concept is without being limited thereto,
And the etchable metal layer including copper of fluorine compounds.
Total amount based on etching agent composite, the amount for the fluorine compounds that may include are about 0.01wt% to about 2wt%.Example
Such as, the amount for the fluorine compounds that may include based on the total amount of etching agent composite, the etching agent composite of embodiment is about
0.01wt% to about 1wt%.Especially, based on the total amount of etching agent composite, the etching agent composite of embodiment may include
The amounts of fluorine compounds be about 0.05wt% to about 0.7wt%.
If the amount of fluorine compounds is greater than about 2wt%, the metal layer including titanium can be by overetch, and can include titanium
Metal layer bottom generate undercutting (undercut), and substrate that can in addition below etching isolation layer or metal layer.In addition, such as
The amount of fruit fluorine compounds is less than about 0.01wt%, then the etching of the metal layer including titanium may cannot achieve.
Fluorine compounds can be hydrogen fluoride (HF), ammonium fluoride (NH4F), potassium fluoride (KF), sodium fluoride (NaF), ammonium acid fluoride
(F2H5N), potassium hydrogen fluoride (KHF2) or sodium bifluoride (NaHF2).The etching agent composite of embodiment may include hydrogen fluoride
(HF), ammonium fluoride (NH4F), potassium fluoride (KF), sodium fluoride (NaF), ammonium acid fluoride (F2H5N), potassium hydrogen fluoride (KHF2) and fluorination
Hydrogen sodium (NaHF2) at least one of be used as fluorine compounds.For example, the etching agent composite of embodiment may include hydrogen fluoride
(HF), ammonium fluoride (NH4F), potassium fluoride (KF), sodium fluoride (NaF), ammonium acid fluoride (F2H5N), potassium hydrogen fluoride (KHF2) and fluorination
Hydrogen sodium (NaHF2) any one of or two or more as fluorine compounds.
The etching agent composite of embodiment can further comprise the three-azo-cycle compounds with sulfydryl.Three-azo-cycle chemical combination
Object means that wherein three cyclic atoms are the compound of nitrogen-atoms.The etching agent composite of embodiment consists essentially of sulfydryl
(- SH), and may include the three-azo-cycle compounds that wherein three ring member nitrogen atoms are nitrogen-atoms.Three-azo-cycle compounds can be substitution
Or unsubstituted triazole compounds.For example, three-azo-cycle compounds can be substituted or unsubstituted triazole compounds and may include
Sulfydryl is as substituent group.
Oxygen radical can be played including the three-azo-cycle compounds with sulfydryl in the etching agent composite of embodiment
The effect of scavenger, removal etch the oxygen radical generated during copper metal layer.Include in the etching agent composite of embodiment
Persulfate in addition to potentiometric titrations also generate oxygen radical, and generated during the etch process of copper metal layer
Carbonyl cycle compound can be attacked and be decomposed to oxygen radical.In addition, carbonyl may be cannot achieve if carbonyl cycle compound is decomposed
The function as the potentiometric titrations scavenger for inhibiting to decompose four-azo-cycle compounds of basic ring compound, and etch
The etching performance of agent composition may decline.That is, the etching agent composite of embodiment includes the three-azo-cycle chemical combination with sulfydryl
Object, and the decomposition of carbonyl cycle compound and four-azo-cycle compounds can be prevented, and etching performance can be improved.
Total amount based on etching agent composite, the amount for the three-azo-cycle compounds that may include are about 0.01wt% to about
1wt%.For example, the total amount based on etching agent composite, the three-azo-cycle compounds that the etching agent composite of embodiment may include
Amount be about 0.01wt% to about 0.5wt%.Especially, based on the total amount of etching agent composite, the etchant group of embodiment
The amount for closing the three-azo-cycle compounds that object may include is about 0.02wt% to about 0.4wt%.
If the amount of three-azo-cycle compounds is greater than about 1wt%, excessive three-azo-cycle compound can be adsorbed to wait lose
On the metal layer at quarter, and the etching performance of etching agent composite may decline.In addition, if the amount of three-azo-cycle compounds is small
In about 0.01wt%, then can not can be removed the oxygen radical generated during etch process, and decomposable carbonyl cycle compound and
Four-azo-cycle compounds, and therefore, the etching quality of etching agent composite may deteriorate.
Meanwhile in the etching agent composite of embodiment, it may include carbonyl cycle compound and three-azo-cycle compounds
Weight ratio is about 1:0.2 to about 1:2.In the etching agent composite of embodiment, it may include carbonyl cycle compound and three-nitrogen
The weight ratio of cycle compound is about 1:0.2 to about 1:2, and can effectively remove the oxygen radical generated during etch process, and
And the decline of etching performance can be prevented.That is, the weight ratio 1 relative to the carbonyl cycle compound with two or more carbonyls,
When the weight ratio of three-azo-cycle compounds is less than 0.2, then the effect of the oxygen free radical scavenger of three-azo-cycle compounds may not
Foot, and carbonyl cycle compound can be decomposed, and therefore, and the etching performance of etching agent composite may deteriorate.In addition, phase
For the weight ratio 1 of the carbonyl cycle compound with two or more carbonyls, when the weight ratio of three-azo-cycle compounds is greater than 2
When, then excessive three-azo-cycle compound can be adsorbed on metal layer and etching performance may deteriorate.
The etching agent composite of embodiment can further comprise disulfate.Disulfate can be used as the erosion of embodiment
Carve the stabilizer of agent composition.In one embodiment, disulfate can be used as the stabilizer of persulfate.For example, sulfuric acid
Hydrogen salt can play the role of preventing etching performance to be in progress with etching, due to persulfate decomposition and decline.That is, disulfate
The decomposition rate of persulfate is reduced, and guarantor can be played in the etch process using the etching agent composite of embodiment
Hold the constant effect of the etch-rate of the metal layer including copper.
In the etching agent composite of embodiment, the total amount based on etching agent composite, the disulfate that may include
Amount is about 0.1wt% to about 5wt%.For example, the total amount based on etching agent composite, the etchant group for the embodiment that may include
The amount for closing object is about 0.2wt% to about 3wt%.
If the amount of disulfate is greater than about 5wt%, it is difficult to control etch-rate, the etching speed of the metal layer including copper
Rate sharply increases, and there may be corrosion defaults.In addition, may not be shown if the amount of disulfate is less than about 0.1wt%
Show the decomposition inhibiting effect of persulfate, and the stability of the etching agent composite of embodiment may deteriorate.
Disulfate can be ammonium hydrogen sulfate (NH4HSO4), lithium hydrogen sulfate (LiHSO4), potassium acid sulfate (KHSO4) or hydrogen sulfate
Sodium (NaHSO4).The etching agent composite of embodiment may include ammonium hydrogen sulfate (NH4HSO4), lithium hydrogen sulfate (LiHSO4), sulfuric acid
Hydrogen potassium (KHSO4) and sodium bisulfate (NaHSO4At least one of).For example, the etching agent composite of embodiment may include sulphur
Sour hydrogen ammonium (NH4HSO4), lithium hydrogen sulfate (LiHSO4), potassium acid sulfate (KHSO4) and sodium bisulfate (NaHSO4Any one of),
Or two or more.
The etching agent composite of embodiment can further comprise sulfoacid compound.Sulfoacid compound can be used as assisted oxidation
Agent.Sulfoacid compound can be played for supplementing the oxidizing force declined with etch process and the erosion for keeping embodiment
Carve the effect of the buffer of the etch-rate of agent composition.The etching agent composite of embodiment, which can play, increases layers of copper and titanium layer
Etching ratio effect.
In the etching agent composite of embodiment, the total amount based on etching agent composite, the sulfoacid compound that may include
Amount be about 0.1wt% to about 5wt%.For example, the total amount based on etching agent composite, the etchant for the embodiment that may include
The amount of composition is about 0.5wt% to about 3wt%.Especially, based on the total amount of etching agent composite, the embodiment that may include
The amount of etching agent composite be about 1wt% to about 3wt%.
If the amount of sulfoacid compound is greater than about 5wt%, the concentration of copper ion can change with the progress of etch process
Become, and therefore, etch-rate may gradually increase.In addition, being etched if the amount of sulfoacid compound is less than about 0.1wt%
Rate may decline with the progress of etch process, and etching performance may deteriorate.
Sulfoacid compound may include sulfamic acid (H3NSO3), ichthyodin, cyclic annular sulfoacid compound or based on the sulfonated of hydrocarbon
Close object.The etching agent composite of embodiment may include sulfamic acid, ichthyodin, cyclic annular sulfoacid compound and the sulfonic acid based on hydrocarbon
At least one of compound.
In addition, cyclic annular sulfoacid compound can be the cyclic annular sulfoacid compound of 1 to 20 carbon atom.For example, cyclic annular sulfonated
The carbon number for closing object can be 2 to 10, and more specifically, the carbon number of cyclic annular sulfoacid compound can be 3 to 6.Cyclic annular sulfoacid compound
It may include propane sultone, butane sultones or propene sultone.
The carbon number of sulfoacid compound based on hydrocarbon can be 1 to 20.For example, the carbon number of the sulfoacid compound based on hydrocarbon can be 2
To 10, and more specifically, the carbon number of the sulfoacid compound based on hydrocarbon can be 3 to 6.Sulfonic acid based on hydrocarbon may include Loprazolam
(CH3SO3H), ethane sulfonic acid (CH3CH2SO3H), benzene sulfonic acid (C6H6SO3) or p-methyl benzenesulfonic acid (p-CH H3C6HSO3H)。
The etching agent composite of embodiment may include sulfamic acid, ichthyodin, propane sultone, in butane sulfonic acid
Any one of ester, propene sultone, Loprazolam, ethane sulfonic acid, benzene sulfonic acid and toluenesulfonic acid or two or more
Kind.
The etching agent composite of embodiment can further comprise phosphoric acid (H3PO4) or phosphate.Phosphoric acid or phosphate can wrap
It is contained in etching agent composite and can control the galvano-cautery of layers of copper or titanium layer.That is, phosphoric acid or phosphate, as between copper and titanium
Current controller, can reduce electronics from include titanium metal layer to the transmission rate for the metal layer for including copper, and can reduce
Due to overetched deflection and it can reduce cone angle.Phosphoric acid or phosphate can play the role of controlling etching performance, so that copper
Layer and titanium layer can have small cone angle.In addition, cone angle is positively retained at constant angle although etching agent composite is reused
Spend and can be improved the service life of etching agent composite.
Total amount based on etching agent composite, the phosphoric acid or phosphatic amount that the etching agent composite of embodiment may include
It is about 0.01wt% to about 5wt%.For example, the total amount based on etching agent composite, the etching agent composite of embodiment can be wrapped
The phosphoric acid or phosphatic amount contained is about 0.1wt% to about 2wt%.
If the total amount based on etching agent composite, phosphoric acid or phosphatic amount are greater than about 5wt% or are less than about
0.01wt%, then the initial cone angle of layers of copper and titanium layer may become too small, and the volume being routed may reduce to make charge
Mobility deterioration.
For example, phosphate may include ammonium dihydrogen phosphate (NH4H2PO4), sodium dihydrogen phosphate (NaH2PO4) and potassium dihydrogen phosphate
(KH2PO4At least one of).
Meanwhile the etching agent composite of embodiment includes water, and may include water in etching agent composite, so that composition
The compound of etching agent composite and the summation of water become 100wt%.That is, although being not expressly mentioned in present inventive concept,
It may include that water becomes the wt% of remaining ingredient in total etching agent composite except water and the summation of the wt% of water
100wt%.Therefore, water occupies the remainder of the sum of wt% of other components in total etching agent composite except water.Implement
Water used in the etching agent composite of mode can be the water with semiconductor or ultrapure water degree.
The etching agent composite of embodiment may include about 5wt% to the persulfate of about 20wt%, about 0.1wt% to about
The carbonyl cycle compound with two or more carbonyls of the four-azo-cycle compounds of 2wt%, about 0.01wt% to about 3wt%,
About 0.01wt% is to the fluorine compounds of about 2wt%, the three-azo-cycle compounds with sulfydryl of about 0.01wt% to about 1wt%, about
0.1wt% is to the disulfate of about 5wt%, about 0.1wt% to the sulfoacid compound of about 5wt%, about 0.01wt% to about 5wt%
Phosphoric acid or phosphate and surplus water.
The etching agent composite of embodiment is used to manufacture the technique of electronic device, for example, by manufacture electronic device
The metal layer of period etch stack and the technique for forming metal pattern.Especially, the etching agent composite of embodiment can be used for
The technique that array substrate is manufactured in the technique of manufacture display device, and be used especially for being made of by etching titanium and copper
It is double-deck and form gate electrode etc..
The etching agent composite of embodiment is the etching agent composite of non-hydroperoxide kind, which includes
Persulfate is as main component, and the metal manufactured by using the etch process of the etching agent composite of embodiment
Pattern displaying goes out excellent etching characteristic, including small critical dimension (CD) deflection and small cone angle.In addition, the erosion of embodiment
Carving agent composition can be used for etching the multilayer for wherein stacking titanium layer and layers of copper in batch mode, and can make to sink during etch process
The generation in shallow lake minimizes and increases the number of etching agent composite reuse.
Hereafter, the method and use for being used to manufacture metal pattern for the illustrative embodiments conceived according to the present invention will be explained
In the method for manufacture array substrate.
Figure 1A to 1E is the cross for the method that display in order manufactures metal pattern using the etching agent composite of embodiment
Section view.Figure 1A to 1E schematically illustrates the cross section in plane, which is parallel to that (it is by third direction axis DR3
Thickness direction) and perpendicular to third direction axis DR3 first direction axis (DR1) limit plane.
Method for manufacturing the metal pattern of embodiment can include: form photosensitive layer in the multilayer for including titanium and copper
The step of pattern；The step of etching agent composite is provided, is formed in the multilayer of light sensitive layer pattern；With removal photosensitive layer figure
The step of case.
Figure 1A to 1C can be shown in the method for manufacturing metal pattern of embodiment in the multilayer including titanium and copper
The step of forming light sensitive layer pattern.Light sensitive layer pattern is formed in the multilayer for including the steps that titanium and copper can include: on substrate
The multilayer for including the steps that titanium and copper is formed, and the step of forming light sensitive layer pattern in multilayer.
Figure 1A can be displayed in the multi-layer C L for being formed on substrate P SB and including the steps that titanium and copper.Figure 1A is shown on substrate P SB
There is provided the first metal layer CL1 and second metal layer CL2 the step of, and the first metal layer CL1 can be include titanium metal layer simultaneously
And second metal layer CL2 can be the metal layer for including copper.Meanwhile Figure 1A shows and wherein stacks the first metal layer CL1 in order
With the bilayer of second metal layer CL2, but the embodiment of present inventive concept is without being limited thereto.Multilayer including titanium and copper can serve as reasons
Be alternately stacked three layers or more of the single layer or in which titanium coating and copper metal layer of composition of alloy including titanium and copper it is more
Layer.
Meanwhile substrate P SB can be insulating substrate.Alternatively, substrate P SB can be array during the manufacturing process of embodiment
Substrate.For example, substrate P SB can be incomplete array substrate, and can be for by forming local circuit layer on basal substrate
And the array substrate in the intermediate steps obtained.Especially, substrate P SB can in the display device of embodiment array of display base
A part (Fig. 3) of plate SUB1, this will be explained later on.For example, substrate P SB can indicate the first basal substrate BS1 (Fig. 3).
It is formed after multi-layer C L on substrate P SB as shown in Figure 1A, photosensitive layer PR is provided and is formed on substrate P SB
Multi-layer C L whole surface on, and by mask MSK exposed photosensitive layer PR, as shown in fig. 1b.
Mask MSK can be by stopping the first component M1 of all radiant lights and transmitting a part of light and stop a part of light
Second component M2 composition.Substrate P SB and multi-layer C L can be divided into the first area for respectively corresponding first component M1 and second component M2
R1 and second area R2.
Then, after the photosensitive layer PR by mask MSK development exposure, as is shown in fig. 1C, with specific thicknesses
Light sensitive layer pattern PRP can be retained in the blocking due to mask MSK and cannot provide for it on first area R1 of light, and can be complete
Photosensitive layer in full removal second area R2, light pass through the second component M2 to second area R2 of mask MSK and expose substrate P SB
Surface.Meanwhile when reference Figure 1B and Fig. 1 C are explained, explain as an embodiment using for removing photosensitive layer
The case where just photosensitive solution of expose portion, but the embodiment of present inventive concept is without being limited thereto.In one embodiment,
The unexposed portion for removing photosensitive layer can be used bears photosensitive solution.
Next, light sensitive layer pattern PRP can be used to pattern the first metal layer CL1 and second metal layer CL2.Photosensitive layer
Pattern P RP can be used as making the patterned mask layer of metallic multilayer CL.That is, as is shown in fig. 1C, etching agent composite (does not show
It can provide and be formed on the multi-layer C L of light sensitive layer pattern PRP out), and by provided etching agent composite, can lose
The multi-layer C L of not formed light sensitive layer pattern PRP thereon is carved, to form metal pattern ML as shown in Figure 1 D.Metal pattern ML can
Including the first metal pattern ML1 and the second metal pattern ML2.In one embodiment, the first metal pattern ML1 can be titanium
Belong to layer, and the second metal pattern ML2 can be copper metal layer.
Embodiment for manufacture the etching agent composite provided in the method for metal pattern may include persulfate,
Four-azo-cycle compounds, carbonyl cycle compound, fluorine compounds and water with two or more carbonyls.Embodiment is used for
Manufacture metal pattern method used in etching agent composite may include persulfate, four-azo-cycle compounds, tool there are two or
Carbonyl cycle compound, fluorine compounds, the three-azo-cycle compounds with sulfydryl, the disulfate, sulfonic acid chemical combination of more carbonyls
The water of object, phosphoric acid or phosphate and surplus.Embodiment is used to manufacture etchant group used in the method for metal pattern
Closing object may include about 5wt% to the persulfate of about 20wt%, the four-azo-cycle compounds of about 0.1wt% to about 2wt%, about
The fluorine with the carbonyl cycle compound of two or more carbonyls, about 0.01wt% to about 2wt% of 0.01wt% to about 3wt%
The sulfuric acid with three-azo-cycle compounds of sulfydryl, about 0.1wt% to about 5wt% of compound, about 0.01wt% to about 1wt%
Hydrogen salt, about 0.1wt% are to the sulfoacid compound of about 5wt%, the phosphoric acid or phosphate and surplus of about 0.01wt% to about 5wt%
Water.
The etching agent composite of embodiment can etch the first metal layer CL1 and second metal layer CL2 in batch mode,
To form metal pattern ML.
With reference to Fig. 1 D and 1E, light sensitive layer pattern PRP and metal pattern ML are by first direction axis DR1 and third direction axis
There can be trapezoidal shape on the cross section that DR3 is limited.However, the embodiment of present inventive concept is without being limited thereto.
Meanwhile the maximum width W2 of metal pattern ML is smaller than the maximum width W1 of light sensitive layer pattern PRP.Meanwhile making
In etch process with photosensitive layer pattern P RP, the maximum width W2 of the maximum width W1 and metal pattern ML of light sensitive layer pattern PRP
Between difference (W1-W2) be defined as critical dimension (CD) deflection, and in Fig. 1 D, " CD1 " or " CD2 " corresponding side CD is inclined
Tiltedly.
After forming metal pattern ML using light sensitive layer pattern PRP, light sensitive layer pattern PRP can remove.Fig. 1 E is shown
Remove the final metal pattern ML after light sensitive layer pattern PRP.Metal pattern ML can be golden wherein to stack titanium metal patterns and copper
The multiple layer metal pattern of metal patterns.
In the method for manufacturing metal pattern of embodiment according to the present invention, metal pattern by the first metal and
Second metal composition, that is, titanium/copper double-level-metal pattern can be manufactured.Referring to figs. 1A to Fig. 1 E explain when, explanation be used to form by
The method of the metal pattern of multiple layers of composition, but the embodiment of present inventive concept is without being limited thereto.Substantially phase can also be passed through
The metal pattern that same method manufacture is formed by the single layer including copper.
Fig. 2 is the plan view for showing a pixel of display device, and the display device includes the use by embodiment
In the array substrate of the method manufacture of manufacture array substrate.Fig. 3 is the cross-sectional view intercepted along the line I-I ' of Fig. 2.Hereafter, will
It is explained referring to figs. 2 and 3 by the array substrate of the method manufacture for manufacturing array substrate of embodiment and equipped with this
The display device of array substrate.
The method for manufacturing array substrate of embodiment can include: grid line and and grid are formed on basal substrate
The step of gate electrode of line connection；Formed in an insulated state across the data line of grid line, the source electrode being connect with data line and
The step of drain electrode separated with source electrode；With the step of forming the pixel electrode connecting with drain electrode.In this case, shape
The step of at grid line and gate electrode connected to the gate line can include: form light sensitive layer pattern in the multilayer for including titanium and copper
The step of；The step of etching agent composite is provided, is formed in the multilayer of light sensitive layer pattern；With removal light sensitive layer pattern
Step.
Meanwhile embodiment for manufacture the etching agent composite in the method for array substrate may include persulfate,
Four-azo-cycle compounds, the carbonyl cycle compound with two or more carbonyls, fluorine compounds, the three-azo-cycles with sulfydryl
Close the water of object, disulfate, sulfoacid compound, phosphoric acid or phosphate and surplus.Embodiment is used to manufacture array substrate
Method used in etching agent composite may include about 5wt% to the persulfate of about 20wt%, about 0.1wt% to about
The carbonyl cycle compound with two or more carbonyls of the four-azo-cycle compounds of 2wt%, about 0.01wt% to about 3wt%,
About 0.01wt% is to the fluorine compounds of about 2wt%, the three-azo-cycle compounds with sulfydryl of about 0.01wt% to about 1wt%, about
0.1wt% is to the disulfate of about 5wt%, about 0.1wt% to the sulfoacid compound of about 5wt%, about 0.01wt% to about 5wt%
Phosphoric acid or phosphate and surplus water.
It is applicable as including for driving by the array substrate of the method manufacture for manufacturing array substrate of embodiment
The substrate of the electronic circuit of dynamic display device.The type of display device is not specifically limited, but may include, for example, liquid crystal
Showing device, organic light-emitting display device, electrophoretic display apparatus, electrowetting display device, MEMS (MEMS) display device
Deng.
Meanwhile liquid crystal display device is shown as the display device in Fig. 2 and 3, but the embodiment of present inventive concept is not
It is limited to this.For example, display device can be organic light-emitting display device.Meanwhile in the implementation of the display device with multiple pixels
Mode, each pixel are formed by identical structure, and for the ease of explaining, a pixel are shown in Fig. 2 and 3.Meanwhile being
Convenient for explaining, shows in Fig. 2 and to connect with a grid line in gate lines G L and the data line in data line DL
Pixel PX, but the embodiment of present inventive concept is without being limited thereto.For example, a grid line and a data line can be with multiple pictures
Element connection, and a plurality of grid line and multiple data lines can be connect with a pixel.
With reference to Fig. 2 and 3, display device DD may include equipped with the array substrate SUB1 of pixel PX, towards array substrate
The opposite substrate SUB2 of the SUB1 and liquid crystal layer LC being arranged between array substrate SUB1 and opposite substrate SUB2.
In order to explain with reference to Fig. 2 and 3, gate lines G L extends and provides on second direction axis DR2.Gate lines G L can be
It is formed on one basal substrate BS1.Data line DL can extend and provide on the first direction axis DR1 perpendicular to gate lines G L.
Pixel PX respectively includes thin film transistor (TFT) TFT, the pixel electrode PE and storage electrode that connect with thin film transistor (TFT) TFT
Component.Thin film transistor (TFT) TFT includes gate electrode GE, gate insulation layer GI, semiconductor pattern SM, source electrode SE and drain electrode DE.It deposits
Storage electrod assembly can further comprise: the storage line SLn extended on second direction axis DR2, and simultaneously from storage line SLn branch
And the first branch electrodes LSLn and the second branch electrodes RSLn extended on axis DR1 in a first direction.
Gate electrode GE can be stretched out from gate lines G L or be provided on the partial region of gate lines G L.Gold can be used in gate electrode GE
Belong to and being formed.Nickel, chromium, molybdenum, aluminium, titanium, copper, tungsten or the alloy including it can be used to be formed for gate electrode GE.Gate electrode GE can be used as list
Layer or multilayer are formed using metal.
Semiconductor pattern SM is provided on gate insulation layer GI.Semiconductor pattern SM provides the gate insulation layer in gate electrode GE
GI is arranged in-between.Semiconductor pattern SM partly overlaps with gate electrode GE.Semiconductor pattern SM includes providing in gate insulation layer
Active patterns (not shown) on GI and the ohmic contact layer (not shown) being formed on active patterns.Active patterns can be used non-
Polycrystal silicon film is formed, and n+ amorphous silicon membrane can be used to be formed for ohmic contact layer (not shown).Ohmic contact layer (not shown)
So that the active patterns Ohmic contact between source electrode SE and drain electrode DE respectively.
Source electrode SE is from data line DL branch and provides.Source electrode SE formed on ohmic contact layer (not shown) and with
Gate electrode GE partly overlaps.Data line DL may be provided on the wherein gate insulation layer GI of not set semiconductor pattern SM.
Drain electrode DE is separated with source electrode SE, and semiconductor pattern SM is arranged in-between.Drain electrode DE is in ohmic contact layer
It is formed on (not shown) and is partly overlapped with gate electrode GE.
In one embodiment, gate lines G L and gate electrode GE are formed as including the metal layer of cupric and the gold of titaniferous
Belong to the multilayer of layer.That is, gate lines G L and gate electrode GE can be the double-level-metal pattern of titanium metal patterns and copper metal pattern, lead to
Titanium coating and copper metal layer that overetch stacks in order and formed.However, the embodiment of present inventive concept is without being limited thereto.
For example, gate lines G L and gate electrode GE can be the metal pattern of the single layer formed using the alloy of titanium and copper, or by stacking three
The titanium metal patterns and copper metal pattern of layer or more and the multiple layer metal pattern that obtains.
In one embodiment, gate lines G L and gate electrode GE can be by using the etching agent composites of embodiment
Etch process is patterned and is formed.In the method for manufacturing array substrate of embodiment, the etching of embodiment is used
Agent composition, metal pattern is formed as during double-deck patterning of titanium coating and copper metal layer, inclined with small CD
Inclined value and small cone angle, so that gate lines G L and gate electrode GE can have excellent taper profile.
In addition, the etching agent composite of embodiment can mention in the method for manufacturing array substrate of embodiment
For the gate electrode GE with small-angle, and then by stacking the gate insulation layer GI formed, semiconductor pattern SM, source electrode SE
There can be excellent stepcoverage with drain electrode DE.
It can be about 30 degree to about by using the cone angle that the etching agent composite of embodiment etches the gate electrode GE to be formed
60 degree.For example, the cone angle of gate electrode GE can be about 40 degree to about 45 degree.
In one embodiment, the insulating layer PSV of array substrate SUB1 can cover source electrode SE, drain electrode DE, channel
Component and gate insulation layer GI, and can have the contact hole CH of part exposure drain electrode DE.Insulating layer PSV may include for example nitrogenizing
Silicon or silica.
Pixel electrode PE is connect by the contact hole CH formed in insulating layer PSV with drain electrode DE.Use transparent conduction
Material forms pixel electrode PE.Especially, pixel electrode PE is formed using transparent conductive oxide.Transparent conductive oxide
It can be tin indium oxide (ITO), indium zinc oxide (IZO), indium tin zinc oxide (ITZO) etc..
That is, array substrate SUB1 may include the thin film transistor (TFT) TFT being formed on the first basal substrate BS1, absolutely
Edge layer PSV and pixel electrode PE.Meanwhile although attached be not shown in the figure, array substrate SUB1 can further comprise being formed in
Oriented layer (not shown) on pixel electrode PE.
Opposite substrate SUB2 may be configured as in face of array substrate SUB1, and may include the second basal substrate BS2, setting
Colour filter CF below the second basal substrate BS2, the light blocking part B M being arranged between the colour filter CF for realizing different colours
(for stopping light) and the common electrode CE that electric field is formed with pixel electrode PE.Meanwhile although attached be not shown in the figure, take
It can be further disposed at below common electrode CE to layer (not shown).
In the method for manufacturing array substrate of embodiment, grid line and gate electrode can be formed, is made it have small
Cone angle, and excellent metal pattern is formed by using the etching agent composite of embodiment, the etching agent composite
Including persulfate, four-azo-cycle compounds, the carbonyl cycle compound with two or more carbonyls, fluorine compounds, there is mercapto
Three-azo-cycle compounds, disulfate, sulfoacid compound, phosphoric acid or the phosphate of base and the water of surplus.
[embodiment]
Hereafter, the etching characteristic of the etching agent composite of reference implementation example and comparative example specific explanations embodiment and will make
The metal pattern manufactured with the etching agent composite.However, etching agent composite in embodiment and the gold using its formation
Metal patterns are merely illustrative, and embodiment does not limit the range of embodiment.
(preparation of etching agent composite)
Using configuration preparation shown in following table 1 according to the etching agent composite of embodiment 1 to 17 and according to comparative example 1
To 9 etching agent composite.Indicate that the unit of the amount of each component indicates the total amount relative to etching agent composite in table 1
The wt% of 100wt%.In table 1, the surplus of the 100wt% of the total amount relative to etching agent composite corresponds to water.
[table 1]
In embodiment and comparative example shown in table 1, ammonium persulfate is used as persulfate, and Aminotetrazole is used as four-nitrogen
Cycle compound, hydantoins are used as carbonyl cycle compound, and ammonium acid fluoride is used as fluorine compounds, 3- amino-1,2,4-triazole -5- sulphur
Alcohol is used as three-azo-cycle compounds, and sodium bisulfate is used as disulfate, and sulfamic acid is used as sulfoacid compound, and selects and make
Use phosphoric acid as phosphoric acid or phosphate.
Etching agent composite shown in embodiment 1 to 17 includes the persulfate, about of about 5wt% to about 20wt%
Four-the azo-cycle compounds of 0.1wt% to about 2wt%, and about 0.01wt% to about 3wt% with two or more carbonyls
Carbonyl cycle compound, and corresponding wherein four-azo-cycle compounds and the carbonyl cycle compound with two or more carbonyls
The case where weight ratio is about 1:0.1 to about 1:2.
Especially, it includes about 5wt% to about 20wt%'s that the etching agent composite of embodiment 1 to 5 shown in table 1 is corresponding
Persulfate, about 0.1wt% to the four-azo-cycle compounds of about 2wt%, about 0.01wt% to about 3wt% tool there are two or more
The carbonyl cycle compound of multiple carbonyls, about 0.01wt% are to the fluorine compounds of about 2wt%, the tool of about 0.01wt% to about 1wt%
There are the three-azo-cycle compounds, about 0.1wt% to the disulfate of about 5wt%, about 0.1wt% of sulfydryl sulfonated to about 5wt%'s
Close phosphoric acid or the phosphatic situation of object and about 0.01wt% to about 5wt%.In addition, in embodiment 1 to 5 as shown in table 1
Etching agent composite in, the weight ratio of four-azo-cycle compounds and carbonyl cycle compound meets the range of about 1:0.1 to about 1:2,
And the weight ratio of carbonyl cycle compound and three-azo-cycle compounds with two or more carbonyls meets about 1:0.2 to about
The range of 1:2.
When compared with embodiment 1 to 5, the correspondence of embodiment 6 does not include phosphoric acid or phosphatic situation, and embodiment 7
Corresponding includes excessive phosphoric acid or phosphatic situation.Embodiment 8 is corresponding wherein relative to two or more carbonyls
The case where weight ratio 1 of carbonyl cycle compound, the weight ratio of three-azo-cycle compounds is less than 0.2, and embodiment 9 is corresponding wherein
Relative to the weight ratio 1 of the carbonyl cycle compound with two or more carbonyls, the weight ratio of three-azo-cycle compounds is greater than 2
The case where.Embodiment 10 is corresponding not to include the case where disulfate, and it includes excessive disulfate that embodiment 11 is corresponding
Etching agent composite.Embodiment 12 is corresponding not to include the case where three-azo-cycle compounds, and it does not include fluorination that embodiment 13 is corresponding
The case where closing object.Embodiment 14 is corresponding to include the case where excessive fluorine compounds, and corresponding embodiment 15 includes excessive three-azo-cycle
The case where compound, embodiment 16 is corresponding not to include the case where sulfoacid compound, and it includes excessive sulphur that embodiment 17 is corresponding
The etching agent composite of acid compound.
Comparative example 1 is corresponding wherein relative to the weight ratio 1 of four-azo-cycle compounds, the carbonyl with two or more carbonyls
The case where weight ratio of basic ring compound is less than 0.1, and the corresponding wherein weight relative to four-azo-cycle compounds of comparative example 2
Than 1, the weight ratio of the carbonyl cycle compound with two or more carbonyls is greater than 2 etching agent composite.Comparative example 3 is corresponding
It does not include the etching agent composite of the carbonyl cycle compound with two or more carbonyls, the correspondence of comparative example 4 does not wherein include
Carbonyl cycle compound with two or more carbonyls, and include the case where the carbonyl cycle compound with a carbonyl,
Comparative example 5 is corresponding not to include the case where four-azo-cycle compounds, and the correspondence of comparative example 6 includes the case where a small amount of persulfate.
Comparative example 7 is corresponding to include the case where excessive persulfate, and the correspondence of comparative example 8 includes the case where excessive four-azo-cycle compound,
And the correspondence of comparative example 9 includes the case where the excessive carbonyl cycle compound with two or more carbonyls.
(manufacture and assessment of metal pattern)
Using etching agent composite shown in table 1, test is etched to the bilayer of titanium coating and copper metal layer.It is logical
Overetch test, for aboutTitanium coating peace treatyCopper metal layer bilayer, in about 28 DEG C of temperature strip
The respective etching agent composite of embodiment and comparative example is provided under part, and is based upon the end point determination when being fully etched upper layers of copper
100% overetch point of twice of time (EPD) assesses etch quantity levels of accumulation, the holding degree of initial cone angle and cone angle.
According to the reuse of etchant, regardless of whether keeping etching quality, according to the increase of copper content in etching agent composite, determine
Etch quantity levels of accumulation.
In the following Table 2, the etching quality assessment result of embodiment and comparative example is shown.In table 2, for using reality
The case where applying the respective etching agent composite manufacture metal pattern of example and comparative example, shows etch quantity levels of accumulation, first cone of origin
The holding at angle and cone angle.Etch quantity levels of accumulation, initial cone angle and cone angle holding evaluation criteria content based on following.Separately
Outside, it for etch quantity levels of accumulation, each project of the holding of initial cone angle and cone angle, summarizes excellent, common and poor
Scoring, and the assessment result summarized is shown in Table 2.
<evaluation criteria of etch quantity levels of accumulation>
O (excellent, 2 points): wherein until the Cu ion including about 6,000ppm or more, etching quality is excellent situation
△ (common, 1 point): wherein until including the Cu ion for being more than or equal to about 4,000ppm and being less than about 6,000ppm,
Etching quality is excellent situation
X (poor, 0 point): wherein until including the Cu ion less than about 4,000, etching quality is excellent situation
<evaluation criteria of initial cone angle>
O (excellent, 2 points): greater than be equal to about 40 degree and be less than about 50 degree
△ (common, 1 point): greater than be equal to about 30 degree and be less than about 40 degree, more than or equal to about 50 degree and is less than about 60 degree
X (poor, 0 point): less than about 30 degree, greater than about 60 degree
<evaluation criteria for keeping cone angle>
O (excellent, 2 points): wherein until Cu ion becomes about 6,000ppm, and the variation of cone angle is less than about 4 ° the case where
△ (common, 1 point): wherein until Cu ion becomes about 6,000ppm, the variation of cone angle is from about 4 ° to less than about 6 °
The case where
X (poor, 0 point): wherein until Cu ion becomes about 6,000ppm, the variation of cone angle is about 6 ° or bigger
In addition, the electronics that Fig. 4 is shown on the cross section after being etched technique for embodiment 1 to embodiment 5 is swept
MIcrosope image is retouched, and in Fig. 4, " Cu 0ppm " and " Cu 6000ppm " respectively corresponds the etchant wherein initially used
The case where composition and wherein etching agent composite are reused until Cu ion becomes about 6,000ppm the case where.
[table 2]
Reference table 2 as a result, discovery when compared with comparative example 1 to comparative example 9, embodiment 1 to embodiment 17 shows excellent
Different etching characteristic.That is, discovery includes about 5wt% to the persulfate of about 20wt%, the four-nitrogen of about 0.1wt% to about 2wt%
The carbonyl cycle compound with two or more carbonyls of cycle compound and about 0.01wt% to about 3wt%, and four-azo-cycles
The embodiment 1 that the weight ratio of compound and the carbonyl cycle compound with two or more carbonyls is about 1:0.1 to about 1:2 to
The etching agent composite of embodiment 17 shows excellent etch quantity levels of accumulation, initial cone angle and cone angle retention performance.On the contrary,
It is unsatisfactory for including about 5wt% to the persulfate of about 20wt%, the four-azo-cycle compound peace treaties of about 0.1wt% to about 2wt%
The carbonyl cycle compound with two or more carbonyls of 0.01wt% to about 3wt%, and four-azo-cycle compounds and have
The weight ratio of the carbonyl cycle compound of two or more carbonyls is the configuration of the etching agent composite of about 1:0.1 to about 1:2
Comparative example 1 shows the etching quality of deterioration to comparative example 9 when compared with embodiment.
In particular, the etching agent composite of embodiment 1 to 5 include persulfate, four-azo-cycle compounds, tool there are two or
Carbonyl cycle compound, fluorine compounds, three-azo-cycle compounds, disulfate, sulfoacid compound, phosphoric acid or the phosphorus of more carbonyls
Hydrochlorate and water, and include in the proper ratio each component, to show excellent etching characteristic.
When compared with comparative example 2, comparative example 3, comparative example 6, comparative example 8 and comparative example 9, embodiment 1 to embodiment 17
Show excellent etch quantity levels of accumulation.This means that the etching agent composite of embodiment, although reusing, still
With excellent etching process ability.Additionally, it was found that when compared with comparative example 5 to comparative example 9, embodiment 1 to embodiment 5,
Embodiment 8 to embodiment 12 and embodiment 16, which provides, has the metal pattern of appropriate initial cone angle to show excellent erosion
Carve quality.Meanwhile when compared with comparative example 1 to comparative example 4 and comparative example 7 to comparative example 9, embodiment 1 to embodiment 7, reality
It applies example 11 and embodiment 13 shows that the cone angle of excellent metal pattern keeps degree to embodiment 17.
That is, embodiment 1 to embodiment 17 uses the erosion of embodiment when compared with comparative example 1 to comparative example 9
It carves agent composition and the metal pattern with excellent cone angle can be formed.Additionally, it was found that although reusing, embodiment party
The etching agent composite of formula maintains excellent etching quality.
Fig. 5 A and 5B respectively illustrate the electronic scanner microscope image after the etch process of embodiment 2 and comparative example 1.
Fig. 5 A and 5B show the image on the cross section of the metal pattern ML and ML ' that are formed below light sensitive layer pattern PRP and PRP '.
When comparing Fig. 5 A and Fig. 5 B, it is found that the side CD deflection CD1 of the metal pattern ML of embodiment is less than the metal pattern of comparative example
The side CD deflection CD1 ' of ML ', and the cone angle (θ of the metal pattern ML of embodiment1) it is less than the metal pattern ML ' of comparative example
Cone angle (θ1').From as a result, it has been found that, formd when compared with comparative example, in embodiment with smaller CD deviant and smaller
Cone angle excellent metal pattern.
The etching agent composite of embodiment can be used for etching multiple gold of titanium coating and copper metal layer in batch mode
Belong to layer, and although reuses but stable etching characteristic can also be kept.In addition, the etching agent composite of embodiment can incite somebody to action
Cone angle (it is the etching characteristic of metal pattern) remains constant degree or less, can show high etch quantity levels of accumulation,
Excellent cone angle can be kept, and can show excellent etching characteristic.Additionally, it was found that by using the etchant of embodiment
The metal pattern and array substrate of composition manufacture have excellent taper profile.
Embodiment can provide with excellent storage stability and improvement includes the etching of the etching characteristic of the multilayer of copper
Agent composition.
Embodiment can provide the method for manufacturing metal pattern, and which improve productivity and such as short-circuit wiring lacks
It falls into.
Embodiment can provide the method for manufacturing array substrate, and wherein multilayer etc. has cone angle appropriate, and heap
The stepcoverage for the metal layer being stacked in multilayer is excellent.
Although exemplary embodiments of the present invention have been described, however, it is understood that the present invention should not necessarily be limited by these shows
Example property embodiment, but in the spirit and scope of following claimed invention, those of ordinary skill in the art can make
Variations and modifications out.
Claims (20)
1. a kind of etching agent composite, based on the total amount of the etching agent composite, the etching agent composite includes:
The persulfate of 5wt% to 20wt%；
Four-the azo-cycle compounds of 0.1wt% to 2wt%；
The carbonyl cycle compound with two or more carbonyls of 0.01wt% to 3wt%；With
Water,
Wherein the weight ratio of the four-azo-cycle compound and the carbonyl cycle compound is 1:0.1 to 1:2.
2. etching agent composite according to claim 1 further comprises more than or equal to 0.01wt% and being less than 1wt%
Three-the azo-cycle compounds with sulfydryl.
3. etching agent composite according to claim 2, wherein the carbonyl cycle compound and the three-azo-cycle compound
Weight ratio be 1:0.2 to 1:2.
4. etching agent composite according to claim 1 further comprises the disulfate of 0.1wt% to 5wt%.
5. etching agent composite according to claim 1 further comprises the fluorine compounds of 0.01wt% to 2wt%.
6. etching agent composite according to claim 1 further comprises the sulfoacid compound of 0.1wt% to 5wt%.
7. etching agent composite according to claim 1 further comprises the phosphoric acid or phosphoric acid of 0.01wt% to 5wt%
Salt.
8. etching agent composite according to claim 1, further comprises:
The fluorine compounds of 0.01wt% to 2wt%；
Three-the azo-cycle compounds with sulfydryl of 0.01wt% to 1wt%；
The disulfate of 0.1wt% to 5wt%；
The sulfoacid compound of 0.1wt% to 5wt%；With
The phosphoric acid or phosphate of 0.01wt% to 5wt%.
9. etching agent composite according to claim 1, wherein the persulfate includes potassium peroxydisulfate K2S2O8, over cure
Sour sodium Na2S2O8With ammonium persulfate (NH4)2S2O8At least one of.
10. etching agent composite according to claim 1 the, wherein four-azo-cycle compound includes Aminotetrazole, methyl
At least one of tetrazolium and thiopurine methyltransferase tetrazolium.
11. etching agent composite according to claim 1, wherein the carbonyl cycle compound includes thiazolidinedione, second
At least one of interior uride and succinimide.
12. etching agent composite according to claim 5, wherein the fluorine compounds include hydrogen fluoride HF, ammonium fluoride
NH4F, potassium fluoride KF, sodium fluoride NaF, ammonium acid fluoride F2H5N, potassium hydrogen fluoride KHF2With sodium bifluoride NaHF2At least one of.
13. etching agent composite according to claim 2 the, wherein three-azo-cycle compounds with sulfydryl include 3-
In sulfydryl -4- methyl -4H-1,2,4- triazole, 3- amino -1,2,4- triazole -5- mercaptan and 1H-1,2,4- triazole -3- mercaptan
It is at least one.
14. etching agent composite according to claim 4, wherein the disulfate includes ammonium hydrogen sulfate NH4HSO4, sulphur
Sour hydrogen lithium LiHSO4, potassium acid sulfate KHSO4With sodium bisulfate NaHSO4At least one of.
15. etching agent composite according to claim 6, wherein the sulfoacid compound include Loprazolam, benzene sulfonic acid,
P-methyl benzenesulfonic acid, ichthyodin, sulfamic acid, cyclic annular at least one of sulfoacid compound and the sulfoacid compound based on hydrocarbon.
16. a kind of method for manufacturing metal pattern, which comprises
Light sensitive layer pattern is formed in the multilayer for including titanium and copper；
It is formed in the multilayer of the light sensitive layer pattern and etching agent composite is provided；With
The light sensitive layer pattern is removed,
Wherein the etching agent composite includes persulfate, four-azo-cycle compounds, the carbonyl with two or more carbonyls
Cycle compound and water, and
The weight ratio of the four-azo-cycle compound and the carbonyl cycle compound is 1:0.1 to 1:2.
17. the method according to claim 16 for manufacturing metal pattern, wherein the multilayer includes:
The first metal layer including titanium；With
It is arranged on the first metal layer and the second metal layer including copper,
Wherein the etching agent composite etches the first metal layer and the second metal layer in batch mode.
18. the method according to claim 16 for manufacturing metal pattern, wherein
The etching agent composite further comprises three-azo-cycle compounds, disulfate, fluorine compounds, the sulfonic acid with sulfydryl
Compound and phosphoric acid or phosphate, and
Based on the total amount of the etching agent composite, the etching agent composite includes:
The persulfate of 5wt% to 20wt%；
Four-the azo-cycle compound of 0.1wt% to 2wt%；
The carbonyl cycle compound of 0.01wt% to 3wt%；
The fluorine compounds of 0.01wt% to 2wt%；
Three-the azo-cycle compound of 0.01wt% to 1wt%；
The disulfate of 0.1wt% to 5wt%；
The sulfoacid compound of 0.1wt% to 5wt%；
The phosphoric acid or the phosphate of 0.01wt% to 5wt%；With
The water of surplus.
19. a kind of method for manufacturing array substrate, which comprises
The gate electrode for forming grid line on substrate and being connect with the grid line；
Formed in an insulated state across the data line of the grid line, the source electrode being connect with the data line, and with the source
The separated drain electrode of electrode；With
The pixel electrode connecting with the drain electrode is formed,
Wherein the gate electrode for forming the grid line and connecting with the grid line includes:
Light sensitive layer pattern is formed in the multilayer for including titanium and copper；
It is formed in the multilayer of the light sensitive layer pattern and etching agent composite is provided；With
The light sensitive layer pattern is removed,
Wherein the etching agent composite includes persulfate, four-azo-cycle compounds, the carbonyl with two or more carbonyls
Cycle compound and water, and the weight ratio of the four-azo-cycle compound and the carbonyl cycle compound is 1:0.1 to 1:2.
20. the method according to claim 19 for manufacturing array substrate, wherein
The etching agent composite further comprises three-azo-cycle compounds, disulfate, fluorine compounds, the sulfonic acid with sulfydryl
Compound and phosphoric acid or phosphate, and
Based on the total amount of the etching agent composite, the etching agent composite includes:
The persulfate of 5wt% to 20wt%；
Four-the azo-cycle compound of 0.1wt% to 2wt%；
The carbonyl cycle compound of 0.01wt% to 3wt%；
The fluorine compounds of 0.01wt% to 2wt%；
Three-the azo-cycle compound of 0.01wt% to 1wt%；
The disulfate of 0.1wt% to 5wt%；
The sulfoacid compound of 0.1wt% to 5wt%；
The phosphoric acid or the phosphate of 0.01wt% to 5wt%；With
The water of surplus.
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| KR20230072123A (en) * | 2021-11-17 | 2023-05-24 | 삼영순화(주) | Eco-friendly photoresist stripper composition |
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| US10910412B2 (en) | 2021-02-02 |
| KR102487940B1 (en) | 2023-01-16 |
| CN110284139B (en) | 2022-05-27 |
| US20190288015A1 (en) | 2019-09-19 |
| KR20190110171A (en) | 2019-09-30 |
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